CN105582918B - Catalyst for dehydrogenation of low-carbon paraffin and application thereof - Google Patents
Catalyst for dehydrogenation of low-carbon paraffin and application thereof Download PDFInfo
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Abstract
The present invention relates to one kind for catalyst for dehydrogenation of low-carbon paraffin and application thereof, mainly solves the problems, such as that the dehydrogenation activity of prior art preparation is lower, stability is poor.The present invention is used for catalyst for dehydrogenation of low-carbon paraffin by using one kind, based on parts by weight, including following components: a) 0.1~5 part of Pt or its oxide；B) 0.1~5 part of Sn of 0.1~5 part of alkali metal or its oxide c) or its oxide；D) 0.1~10 part of Ce-M-O solid solution, M are selected from least one of periodic table of elements group ivb element；E) 80~99 parts of carrier Ss, S are selected from the technical solution of at least one of aluminium oxide, silica or molecular sieve, preferably solve the problems, such as this, can be used for dehydrogenating low-carbon alkane and prepare in low-carbon alkene industrial production.
Description
Technical field
The present invention relates to one kind for catalyst for dehydrogenation of low-carbon paraffin and application thereof.
Background technique
Low-carbon alkene, such as propylene and isobutene, are important petrochemical materials, they and ethylene are considered as together
The basis of modern petrochemical is mainly obtained in the form of steam cracking and refinery factory fluid catalytic cracking process by-product/coproduction,
It is difficult to meet increasing rapidly for the market demand.Currently, low-carbon alkanes are directly made mostly in China's natural gas, casing-head gas and refinery gas
For fuel burn-up, it is underutilized, added value is very low.It, can be with if low-carbon alkene effectively can be catalytically converted into for they
It greatly improves the utility value of low-carbon alkanes and the market demand can be met, so the research of dehydrogenating low-carbon alkane technology is constantly subjected to
Pay attention to.Dehydrogenating low-carbon alkane is a strong endothermic reaction, is only possible to obtain at relatively high reaction temperatures more satisfactory
Olefin yields.However excessively high reaction temperature often brings a series of side reactions, to reduce the selectivity of alkene, makes to urge
The problems such as quick carbon distribution in agent surface, inactivation, cause catalyst performance to be deteriorated, and selectivity is lower, it is excellent that therefore, it is necessary to processabilities
Good dehydrogenation improves alkane conversion and olefine selective.
Currently, industrialized dehydrogenating low-carbon alkane technology have the Oleflex technique of UOP, the Catofin technique of Lummus,
The FBD technique etc. that the STAR technique of Uhde, the PDH technique of Linde, Snamprogetti-Yarsintez develop cooperatively, wherein
Industrialized unit it is most be Oleflex technology and Catofin technology, the catalyst of the two application is that Pt system and Cr system urge respectively
Agent, wherein Pt series catalysts become research hotspot because it has the characteristics that high activity, low pollution, low wear rate.In recent years,
There are more document report and patent application in terms of in relation to dehydrating alkanes Pt series catalysts, Wang Jidong etc. is at " modern chemical industry "
Delivered on 2011,31 supplementary issue 1,205-209 " potassium is to Pt-Sn/Al2O3The shadow of catalyst surface acidity and dehydrogenation of isobutane performance
Ring " article discovery discovery be added K the strong L acid amount of catalyst surface can be effectively reduced, it is suppressed that isomery and cracking etc. side reactions, isobutyl
Alkene is selectively significantly increased, and suitable K amount is 0.4-0.8wt%, and the conversion ratio of catalyst is 35% or so at this time, selectivity
It is 95%.Catalyst K-Ce-Pt-Sn/ γ-Al disclosed in Chinese patent (CN200910209534.4)2O3It is small in the reaction time 6
When within, conversion of propane is greater than 38%, and Propylene Selectivity is greater than 98%, and coke content is less, which also mentions
The space risen, does not provide catalyst stability data.Yu etc. in " Applied Catalysis A " (applied catalysis A) 2006,
" the Effects of Ce addition on the Pt-Sn/ γ-Al delivered on 315,58-672O3catalyst for
(addition of Ce is to the Pt-Sn/ γ-for preparing propylene by dehydrogenating propane by propane dehydrogenation to propylene "
Al2O3The influence of catalyst) article discovery Ce be added rear catalyst performance significantly improve, reaction 50 hours in, conversion of propane is big
In 38%, addition of the Propylene Selectivity greater than 98%, Ce not only makes active component stablize the formation for also slowing down carbon deposit, and investigation is urged
Agent regeneration finds that tertiary recycling rear catalyst performance does not change substantially when stablizing.
Catalyst for dehydrogenation of low-carbon paraffin has been achieved with greater advance at present, but there are still conversion ratio is not high or conversion ratio
The lower problem of olefine selective in higher situation, stability are also required to further strengthen.The present invention uses Ce-M-O solid solution
It is auxiliary agent with alkali metal element, catalyst surface characteristic can be changed by being added in catalyst, to improve the performance of catalyst, therefore be had
There is preferable application prospect, there has been no relevant reports at present.
Summary of the invention
The first technical problem to be solved by the present invention is that catalyst for dehydrogenation of low-carbon paraffin activity is lower, steady in the prior art
The problem of qualitative difference provides a kind of new for catalyst for dehydrogenation of low-carbon paraffin.The second technical problem to be solved by the present invention is
There is provided one of one kind and solution technical problem corresponding method for preparing catalyst.
One of to solve above-mentioned technical problem, The technical solution adopted by the invention is as follows: a kind of be used for dehydrogenating low-carbon alkane
Catalyst, based on parts by weight, including following components:
A) 0.1~5 part of Pt or its oxide；
B) 0.1~5 part of alkali metal or its oxide；
C) 0.1~5 part of Sn or its oxide；
D) 0.1~10 part of Ce-M-O solid solution, M are selected from least one of periodic table of elements group ivb element；
E) 80~99 parts of carrier Ss, S are selected from least one of aluminium oxide, silica or molecular sieve.
In above-mentioned technical proposal, based on parts by weight, the preferred scope of Pt or its oxide number is 0.1~2.5 part；Alkali
The preferred scope of metal or its oxide number is 0.5~2 part；The preferred scope of Sn or its oxide number is 0.1~2.5
Part；The preferred scope of Ce-M-O solid solution number is that 1~5, M is preferably Zr and Ti；With Ce:M in molar ratio computing catalyst for (1
~99): 1, preferably (3~9): 1；Carrier S is γ-Al2O3、SiO2, ZSM-5, SAPO-34, SBA-15 and MCM-41 at least
It is a kind of.With Pt:Sn in molar ratio computing catalyst for (0.01~5): 1.
To solve above-mentioned technical problem two, The technical solution adopted by the invention is as follows: a kind of be used for dehydrogenating low-carbon alkane
Catalyst and preparation method thereof, comprising the following steps:
A) after the carrier S of content needed for weighing is poured into suitable deionized water and stirred 0.5~10 hour, contain needed for weighing
The soluble-salt of the Ce and M of amount are dissolved in respectively in suitable deionized water, are then uniformly mixed the two, pour into carrier and water
In mixed liquor, after continuing stirring 0.5~10 hour, it is slowly dropped into pH adjusting agent under continuous stirring until pH is 7~10；It will produce
Object aging, suction filtration are washed, are dried, roasting and obtain the complex carrier of Ce-M-O solid solution and S；
B) soluble-salt of the desired amount of Sn is dissolved in suitable hydrochloric acid solution, is added what a step obtained under stiring
It in composite carrier, is uniformly mixed, 10~80 DEG C impregnate 1~24 hour, dry, roast to obtain catalyst precarsor I；
C) soluble-salt of the desired amount of Pt and alkali metal are dissolved in suitable water, urging for b step is added under stiring
Agent precursor I is uniformly mixed, and 10~80 DEG C impregnate 1~24 hour, is dried, is roasted to obtain catalyst for dehydrogenation of low-carbon paraffin.
In above-mentioned technical proposal, the soluble-salt of alkali metal, Ce and M be can be selected from chloride, nitrate or acetate
It is a kind of；The preferred chloroplatinic acid of the soluble-salt of Pt；The soluble-salt of tin is selected from one kind of stannous chloride or tin tetrachloride.
Catalyst obtained carries out activity rating in isotherm formula fixed bed reactors according to the above method, de- to low-carbon alkanes
For hydrogen producing light olefins system appraisal, summary process is as follows:
By low-carbon alkanes unstrpped gas by mass flowmenter adjust flow, mixed into pre-add hot-zone, then into
Enter reaction zone, the pre-add hot-zone of reactor and reaction zone are all made of electric-heating-wire-heating, make up to predetermined temperature, reactor it is interior
Diameter is the stainless steel sleeve pipe of Ф 9mm-Ф 6mm, is about 400mm.After gas after reaction passes through drainer, into gas-chromatography
Analyze its composition.Evaluating catalyst condition is as follows in isotherm formula fixed bed reactors: 0.5 gram or so of catalyst is packed into internal diameter
(catalyst bed layer height about 17mm), propane or iso-butane and hydrogen volume ratio are in isothermal reactor for Ф 9mm-Ф 6mm
10:1~1:1, reaction temperature are 400 DEG C~600 DEG C, and reaction pressure is 0~1MPa, and alkane mass space velocity is 3.0~8.0h-1,
Reaction raw materials and the catalyst haptoreaction obtain propylene or isobutene.
During dehydrogenating low-carbon alkane, simple Pt-Sn/Al2O3Catalyst surface acidity is stronger, and catalyst surface is easily long-pending
Carbon and accelerate deactivation rate.To slow down catalyst inactivation speed, catalyst performance can be improved by the way that other auxiliary agents are added, simultaneously
Reaction temperature can also be reduced and mitigate catalyst surface carbon distribution.Compared with prior art, the present invention has the advantages that significant and protrusion
Property effect, the addition of alkali metal element can reduce its catalyst surface acidity, and the addition of cerium zirconium sosoloid can improve Pt element and exist
Dispersion on carrier, or promote the formation of more active sites Pt, to improve Pt series catalysts carbon accumulation resisting ability, and enhance Sn
The effect of component and carrier, to improve catalyst performance.Catalyst of the invention is used for using above-mentioned evaluation condition low
In carbon alkane dehydrogenation reaction, Activity evaluation shows catalyst alkane conversion with higher, compared with low reaction temperatures
Lower to reach 54%, while selectivity with higher up to iso-butane conversion ratio, selective isobutene is greater than 93%, and passes through 20
Secondary rear catalyst conversion ratio of making charcoal still has 52%, is selectively still greater than 93%, achieves preferable technical effect.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
[embodiment 1]
It weighs after 9.36g alumina support pours into 200mL deionized water and stir 1 hour, weighing 1.081g ammonium ceric nitrate
It is dissolved in 50mL deionized water with 0.212g zirconium nitrate, is then uniformly mixed the two respectively, pour into the mixing of aluminium oxide and water
In liquid, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product aging 2 hours, with 2L water
Filtering and washing obtains filter cake, by filter cake at 90 DEG C after dry 16 hours, 580 DEG C of Muffle kiln roastings 20 hours to get
Ce0.8Zr0.2O2-Al2O3Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned carrier
In, it is uniformly mixed, 30 DEG C impregnate 12 hours, dry 16 hours at 90 DEG C then up to catalyst precarsor, are denoted as I.It weighs
The chloroplatinic acid of 0.159g and 0.207 potassium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 30 DEG C of dippings 12 are small
When, 90 DEG C drying 16 hours, obtain catalyst for dehydrogenation of low-carbon paraffin at 580 DEG C and be denoted as A within Muffle kiln roasting 20 hours.Catalysis
Agent evaluation condition is as follows: 0.5 gram of catalyst being fitted into above-mentioned isothermal fixed bed reactors (catalyst bed layer height 17mm), instead
Answer normal pressure, 550 DEG C of temperature；Iso-butane and hydrogen volume ratio are 2.5:1；Alkane mass space velocity is 4.6h-1.The result is shown in tables 2.
[embodiment 2]
It weighs after 9.75g alumina support pours into 200mL deionized water and stir 1 hour, weighing 0.027g ammonium ceric nitrate
It is dissolved in 50mL deionized water with 0.005g zirconium nitrate, is then uniformly mixed the two respectively, pour into the mixing of aluminium oxide and water
In liquid, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product aging 2 hours, with 2L water
Filtering and washing obtains filter cake, by filter cake at 90 DEG C after dry 16 hours, 580 DEG C of Muffle kiln roastings 20 hours to get
Ce0.8Zr0.2O2-Al2O3Carrier.It weighs 0.295g tin tetrachloride to be dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned carrier
In, it is uniformly mixed, 10 DEG C impregnate 24 hours, dry 16 hours at 90 DEG C then up to catalyst precarsor, are denoted as I.It weighs
The chloroplatinic acid of 0.159g and 0.207 potassium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 10 DEG C of dippings 24 are small
When, 90 DEG C drying 16 hours, obtain catalyst for dehydrogenation of low-carbon paraffin at 580 DEG C and be denoted as B within Muffle kiln roasting 20 hours.Examination
Condition the results are shown in Table 2 with embodiment 1.
[embodiment 3]
It weighs after 8.76g alumina support pours into 200mL deionized water and stir 1 hour, weighing 2.702g ammonium ceric nitrate
It is dissolved in 50mL deionized water with 0.529g zirconium nitrate, is then uniformly mixed the two respectively, pour into the mixing of aluminium oxide and water
In liquid, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product aging 2 hours, with 2L water
Filtering and washing obtains filter cake, by filter cake at 90 DEG C after dry 16 hours, 580 DEG C of Muffle kiln roastings 20 hours to get
Ce0.8Zr0.2O2-Al2O3Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned carrier
In, it is uniformly mixed, 80 DEG C impregnate 1 hour, dry 16 hours at 90 DEG C then up to catalyst precarsor, are denoted as I.Weigh 0.159g
Chloroplatinic acid and 0.207 potassium nitrate be dissolved in 10mL water, be added with stirring in I, be uniformly mixed, 80 DEG C impregnate 1 hour, 90 DEG C
16 hours dry, at 580 DEG C, i.e. obtaining catalyst for dehydrogenation of low-carbon paraffin is denoted as C within Muffle kiln roasting 20 hours.Examination condition is same
Embodiment 1, the results are shown in Table 2.
[embodiment 4]
It weighs after 9.26g alumina support pours into 200mL deionized water and stir 1 hour, weighing 1.351g ammonium ceric nitrate
It is dissolved in 50mL deionized water with 0.265g zirconium nitrate, is then uniformly mixed the two respectively, pour into the mixing of aluminium oxide and water
In liquid, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product aging 2 hours, with 2L water
Filtering and washing obtains filter cake, by filter cake at 80 DEG C after dry 24 hours, 580 DEG C of Muffle kiln roastings 20 hours to get
Ce0.8Zr0.2O2-Al2O3Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned carrier
In, it is uniformly mixed, 30 DEG C impregnate 12 hours, dry 24 hours at 80 DEG C then up to catalyst precarsor, are denoted as I.It weighs
The chloroplatinic acid of 0.159g and 0.207 potassium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 30 DEG C of dippings 12 are small
When, 80 DEG C drying 24 hours, obtain catalyst for dehydrogenation of low-carbon paraffin at 580 DEG C and be denoted as D within Muffle kiln roasting 20 hours.Examination
Condition the results are shown in Table 2 with embodiment 1.
[embodiment 5]
It weighs after 9.66g alumina support pours into 200mL deionized water and stir 1 hour, weighing 0.270g ammonium ceric nitrate
It is dissolved in 50mL deionized water with 0.053g zirconium nitrate, is then uniformly mixed the two respectively, pour into the mixing of aluminium oxide and water
In liquid, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product aging 2 hours, with 2L water
Filtering and washing obtains filter cake, by filter cake at 150 DEG C after dry 6 hours, 580 DEG C of Muffle kiln roastings 20 hours to get
Ce0.8Zr0.2O2-Al2O3Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned carrier
In, it is uniformly mixed, 30 DEG C impregnate 12 hours, dry 6 hours at 150 DEG C then up to catalyst precarsor, are denoted as I.It weighs
The chloroplatinic acid of 0.159g and 0.207 potassium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 30 DEG C of dippings 12 are small
When, 150 DEG C drying 6 hours, obtain catalyst for dehydrogenation of low-carbon paraffin at 580 DEG C and be denoted as E within Muffle kiln roasting 20 hours.Examination
Condition the results are shown in Table 2 with embodiment 1.
[embodiment 6]
Weigh after 9.36g alumina support pours into 200mL deionized water and stir 1 hour, weigh 1.207 ammonium ceric nitrates with
0.011 zirconium nitrate is dissolved in respectively in 50mL deionized water, is then uniformly mixed the two, pours into the mixed liquor of aluminium oxide and water
In, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product aging 2 hours, taken out with 2L water
Filter washing obtains filter cake, by filter cake at 90 DEG C after dry 16 hours, 580 DEG C of Muffle kiln roastings 20 hours to get
Ce0.99Zr0.01O2-Al2O3Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned load
It in body, is uniformly mixed, 30 DEG C impregnate 12 hours, dry 16 hours at 90 DEG C then up to catalyst precarsor, are denoted as I.It weighs
The chloroplatinic acid of 0.159g and 0.207 potassium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 30 DEG C of dippings 12 are small
When, 90 DEG C drying 16 hours, be denoted as F at 580 DEG C to get to catalyst for dehydrogenation of low-carbon paraffin within Muffle kiln roasting 20 hours.It examines
It comments condition with embodiment 1, the results are shown in Table 2.
[embodiment 7]
It weighs after 9.36g alumina support pours into 200mL deionized water and stir 1 hour, weighing 0.915g ammonium ceric nitrate
It is dissolved in 50mL deionized water with 0.265g zirconium nitrate, is then uniformly mixed the two respectively, pour into the mixing of aluminium oxide and water
In liquid, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product aging 2 hours, with 2L water
Filtering and washing obtains filter cake, by filter cake at 90 DEG C after dry 16 hours, 580 DEG C of Muffle kiln roastings 20 hours to get
Ce0.75Zr0.25O2-Al2O3Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned load
It in body, is uniformly mixed, 30 DEG C impregnate 12 hours, dry 16 hours at 90 DEG C then up to catalyst precarsor, are denoted as I.It weighs
The chloroplatinic acid of 0.159g and 0.207 potassium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 30 DEG C of dippings 12 are small
When, 90 DEG C drying 16 hours, obtain catalyst for dehydrogenation of low-carbon paraffin at 580 DEG C and be denoted as G within Muffle kiln roasting 20 hours.Examination
Condition the results are shown in Table 2 with embodiment 1.
[embodiment 8]
It weighs after 9.36g alumina support pours into 200mL deionized water and stir 1 hour, weighing 1.097g ammonium ceric nitrate
It is dissolved in 50mL deionized water with 0.106g zirconium nitrate, is then uniformly mixed the two respectively, pour into the mixing of aluminium oxide and water
In liquid, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product aging 2 hours, with 2L water
Filtering and washing obtains filter cake, by filter cake at 90 DEG C after dry 16 hours, 580 DEG C of Muffle kiln roastings 20 hours to get
Ce0.9Zr0.1O2-Al2O3Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned carrier
In, it is uniformly mixed, 30 DEG C impregnate 12 hours, dry 16 hours at 90 DEG C then up to catalyst precarsor, are denoted as I.It weighs
The chloroplatinic acid of 0.159g and 0.207 potassium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 30 DEG C of dippings 12 are small
When, 90 DEG C drying 16 hours, obtain catalyst for dehydrogenation of low-carbon paraffin at 580 DEG C and be denoted as H within Muffle kiln roasting 20 hours.Examination
Condition the results are shown in Table 2 with embodiment 1.
[embodiment 9]
It weighs after 9.36g alumina support pours into 200mL deionized water and stir 1 hour, weighing 0.743g ammonium ceric nitrate
It is dissolved in 50mL deionized water with 0.581g zirconium nitrate, is then uniformly mixed the two respectively, pour into the mixing of aluminium oxide and water
In liquid, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product aging 2 hours, with 2L water
Filtering and washing obtains filter cake, by filter cake at 90 DEG C after dry 16 hours, 580 DEG C of Muffle kiln roastings 20 hours to get
Ce0.5Zr0.5O2-Al2O3Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned carrier
In, it is uniformly mixed, 30 DEG C impregnate 12 hours, dry 16 hours at 90 DEG C then up to catalyst precarsor, are denoted as I.It weighs
The chloroplatinic acid of 0.159g and 0.207 potassium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 30 DEG C of dippings 12 are small
When, 90 DEG C drying 16 hours, obtain catalyst for dehydrogenation of low-carbon paraffin at 580 DEG C and be denoted as I within Muffle kiln roasting 20 hours.Examination
Condition the results are shown in Table 2 with embodiment 1.
[embodiment 10]
Weigh after 9.36g alumina support pours into 200mL deionized water and stir 1 hour, weigh 0.776 cerous chloride with
0.099g titanium tetrachloride is dissolved in respectively in 50mL deionized water, is then uniformly mixed the two, pours into the mixing of aluminium oxide and water
In liquid, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product aging 2 hours, with 2L water
Filtering and washing obtains filter cake, by filter cake at 90 DEG C after dry 16 hours, 580 DEG C of Muffle kiln roastings 20 hours to get
Ce0.8Ti0.2O2-Al2O3Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned carrier
In, it is uniformly mixed, 30 DEG C impregnate 12 hours, dry 16 hours at 90 DEG C then up to catalyst precarsor, are denoted as I.It weighs
The chloroplatinic acid of 0.159g and 0.207 potassium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 30 DEG C of dippings 12 are small
When, 90 DEG C drying 16 hours, obtain catalyst for dehydrogenation of low-carbon paraffin at 580 DEG C and be denoted as J within Muffle kiln roasting 20 hours.Examination
Condition the results are shown in Table 2 with embodiment 1.
[embodiment 11]
It weighs after 9.36g alumina support pours into 200mL deionized water and stir 1 hour, weighing 0.663g cerous chloride
It is dissolved in 50mL deionized water with 0.143g hafnium tetrachloride, is then uniformly mixed the two respectively, pour into the mixed of aluminium oxide and water
It closes in liquid, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product aging 2 hours, 2L is used
Water filtering and washing obtains filter cake, by filter cake at 90 DEG C after dry 16 hours, 580 DEG C of Muffle kiln roastings 20 hours to get
Ce0.8Hf0.2O2-Al2O3Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned carrier
In, it is uniformly mixed, 30 DEG C impregnate 12 hours, dry 16 hours at 90 DEG C then up to catalyst precarsor, are denoted as I.It weighs
The chloroplatinic acid of 0.159g and 0.207 potassium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 30 DEG C of dippings 12 are small
When, 90 DEG C drying 16 hours, be denoted as K at 580 DEG C up to catalyst for dehydrogenation of low-carbon paraffin within Muffle kiln roasting 20 hours.Check and rate item
Part the results are shown in Table 2 with embodiment 1.
[embodiment 12]
It weighs after 9.57g alumina support pours into 200mL deionized water and stir 1 hour, weighing 1.081g ammonium ceric nitrate
It is dissolved in 50mL deionized water with 0.212g zirconium nitrate, is then uniformly mixed the two respectively, pour into the mixing of aluminium oxide and water
In liquid, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product aging 1 hour, with 1L water
Filtering and washing obtains filter cake, by filter cake at 90 DEG C after dry 16 hours, 450 DEG C of Muffle kiln roastings 24 hours to get
Ce0.8Zr0.2O2-Al2O3Carrier.It weighs 0.019g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned carrier
In, it is uniformly mixed, 30 DEG C impregnate 12 hours, dry 16 hours at 90 DEG C then up to catalyst precarsor, are denoted as I.It weighs
The chloroplatinic acid and 0.100g lithium nitrate of 0.027g is dissolved in 10mL water, is added with stirring in I, is uniformly mixed, and 30 DEG C of dippings 12 are small
When, 90 DEG C drying 16 hours, obtain catalyst for dehydrogenation of low-carbon paraffin at 450 DEG C and be denoted as L within Muffle kiln roasting 24 hours.Examination
Condition the results are shown in Table 2 with embodiment 1.
[embodiment 13]
It weighs after 8.10g alumina support pours into 200mL deionized water and stir 2 hours, weighing 1.081g ammonium ceric nitrate
It is dissolved in 50mL deionized water with 0.212g zirconium nitrate, is then uniformly mixed the two respectively, pour into the mixing of aluminium oxide and water
In liquid, after continuing stirring 2 hours, ammonium hydroxide is slowly dropped under lasting stirring until pH is 10.By product aging 2 hours, with 2L water
Filtering and washing obtains filter cake, by filter cake at 90 DEG C after dry 16 hours, 650 DEG C of Muffle kiln roastings 6 hours to get
Ce0.8Zr0.2O2-Al2O3Carrier.It weighs 0.951g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned carrier
In, it is uniformly mixed, 30 DEG C impregnate 12 hours, dry 16 hours at 90 DEG C then up to catalyst precarsor, are denoted as I.It weighs
The chloroplatinic acid and 1.848g sodium nitrate of 1.327g is dissolved in 10mL water, is added with stirring in I, is uniformly mixed, and 30 DEG C of dippings 12 are small
When, 90 DEG C drying 16 hours, obtain catalyst for dehydrogenation of low-carbon paraffin at 650 DEG C and be denoted as M within Muffle kiln roasting 6 hours.Examination
Condition the results are shown in Table 2 with embodiment 1.
[embodiment 14]
It weighs after 8.90g alumina support pours into 200mL deionized water and stir 0.5 hour, weighing 1.081g cerous nitrate
Ammonium and 0.212g zirconium nitrate are dissolved in respectively in 50mL deionized water, are then uniformly mixed the two, pour into the mixed of aluminium oxide and water
It closes in liquid, after continuing stirring 0.5 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 7.By product aging 3 hours, 5L is used
Water filtering and washing obtains filter cake, by filter cake at 90 DEG C after dry 16 hours, 580 DEG C of Muffle kiln roastings 20 hours to get
Ce0.8Zr0.2O2-Al2O3Carrier.It weighs 0.475g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned carrier
In, it is uniformly mixed, 30 DEG C impregnate 12 hours, dry 16 hours at 90 DEG C then up to catalyst precarsor, are denoted as I.It weighs
The chloroplatinic acid and 0.345g rubidium nitrate of 0.664g is dissolved in 10mL water, is added with stirring in I, is uniformly mixed, and 30 DEG C of dippings 12 are small
When, 90 DEG C drying 16 hours, obtain catalyst for dehydrogenation of low-carbon paraffin at 580 DEG C and be denoted as N within Muffle kiln roasting 20 hours.Examination
Condition the results are shown in Table 2 with embodiment 1.
[embodiment 15]
It weighs after 9.39g alumina support pours into 200mL deionized water and stir 1 hour, weighing 1.081g ammonium ceric nitrate
It is dissolved in 50mL deionized water with 0.212g zirconium nitrate, is then uniformly mixed the two respectively, pour into the mixing of aluminium oxide and water
In liquid, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product aging 2 hours, with 2L water
Filtering and washing obtains filter cake, by filter cake at 90 DEG C after dry 16 hours, 580 DEG C of Muffle kiln roastings 20 hours to get
Ce0.8Zr0.2O2-Al2O3Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned carrier
In, it is uniformly mixed, 30 DEG C impregnate 12 hours, dry 16 hours at 90 DEG C then up to catalyst precarsor, are denoted as I.It weighs
The chloroplatinic acid of 0.159g and 0.073 cesium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 30 DEG C of dippings 12 are small
When, 90 DEG C drying 16 hours, obtain catalyst for dehydrogenation of low-carbon paraffin at 580 DEG C and be denoted as O within Muffle kiln roasting 20 hours.Examination
Condition the results are shown in Table 2 with embodiment 1.
[embodiment 16]
It weighs after 9.36g alumina support pours into 200mL deionized water and stir 1 hour, weighing 0.755g cerous chloride,
0.082g zirconium oxychloride and 0.048g titanium tetrachloride are dissolved in respectively in 50mL deionized water, are then uniformly mixed three, are poured into
In the mixed liquor of aluminium oxide and water, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product
Aging 2 hours, filter cake is obtained with 2L water filtering and washing, by filter cake after 90 DEG C 16 hours dry, is roasted in 580 DEG C of Muffle furnaces
20 hours are burnt to get Ce0.8Zr0.1Ti0.1O2-Al2O3Carrier.0.190g stannous chloride is weighed to be dissolved in the hydrochloric acid solution of 10mL,
It is added with stirring in above-mentioned carrier, is uniformly mixed, 30 DEG C impregnate 12 hours, before drying 16 hours at 90 DEG C then up to catalyst
Body is denoted as I.The potassium nitrate of the chloroplatinic acid and 0.207g that weigh 0.159g is dissolved in 10mL water, is added with stirring in I, and mixing is equal
Even, 30 DEG C impregnate 12 hours, 90 DEG C drying 16 hours, 580 DEG C Muffle kiln roasting 20 hours be to obtain dehydrogenating low-carbon alkane
Catalyst is denoted as P.Examination condition the results are shown in Table 2 with embodiment 1.
[embodiment 17]
It weighs after 9.31g alumina support pours into 200mL deionized water and stir 1 hour, weighing 1.081g ammonium ceric nitrate
It is dissolved in 50mL deionized water with 0.212g zirconium nitrate, is then uniformly mixed the two respectively, pour into the mixing of aluminium oxide and water
In liquid, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product aging 2 hours, with 2L water
Filtering and washing obtains filter cake, by filter cake at 90 DEG C after dry 16 hours, 580 DEG C of Muffle kiln roastings 20 hours to get
Ce0.8Zr0.2O2-Al2O3Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned carrier
In, it is uniformly mixed, 30 DEG C impregnate 12 hours, dry 16 hours at 90 DEG C then up to catalyst precarsor, are denoted as I.It weighs
The chloroplatinic acid of 0.159g, the potassium nitrate of 0.207g and 0.227g zinc nitrate are dissolved in 10mL water, are added with stirring in I, and mixing is equal
Even, 30 DEG C impregnate 12 hours, 90 DEG C drying 16 hours, 580 DEG C Muffle kiln roasting 20 hours be to obtain dehydrogenating low-carbon alkane
Catalyst is denoted as Q.Examination condition the results are shown in Table 2 with embodiment 1.
[embodiment 18]
Weigh 9.43gSiO2Carrier pours into 200mL deionized water stir 1 hour after, weigh 1.081g ammonium ceric nitrate and
0.212g zirconium nitrate is dissolved in respectively in 50mL deionized water, is then uniformly mixed the two, pours into the mixed liquor of aluminium oxide and water
In, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product aging 2 hours, taken out with 2L water
Filter washing obtains filter cake, by filter cake at 90 DEG C after dry 16 hours, 580 DEG C of Muffle kiln roastings 20 hours to get
Ce0.8Zr0.2O2-SiO2Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned carrier
In, it is uniformly mixed, 30 DEG C impregnate 12 hours, dry 16 hours at 90 DEG C then up to catalyst precarsor, are denoted as I.It weighs
The chloroplatinic acid of 0.159g and the potassium nitrate of 0.026g are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, 30 DEG C of dippings 12
Hour, 90 DEG C drying 16 hours, 580 DEG C Muffle kiln roasting 20 hours be to obtain catalyst for dehydrogenation of low-carbon paraffin and be denoted as R.It examines
It comments condition with embodiment 1, the results are shown in Table 2.
[embodiment 19]
It weighs after 9.43gSBA-15 carrier pours into 200mL deionized water and stir 1 hour, weighing 1.081g ammonium ceric nitrate
It is dissolved in 50mL deionized water with 0.212g zirconium nitrate, is then uniformly mixed the two respectively, pour into the mixing of aluminium oxide and water
In liquid, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product aging 2 hours, with 2L water
Filtering and washing obtains filter cake, by filter cake at 90 DEG C after dry 16 hours, 580 DEG C of Muffle kiln roastings 20 hours to get
Ce0.8Zr0.2O2- SBA-15 carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned load
It in body, is uniformly mixed, 30 DEG C impregnate 12 hours, dry 16 hours at 90 DEG C then up to catalyst precarsor, are denoted as I.It weighs
The chloroplatinic acid of 0.159g and the potassium nitrate of 0.026g are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, 30 DEG C of dippings 12
Hour, 90 DEG C drying 16 hours, 580 DEG C Muffle kiln roasting 20 hours be to obtain catalyst for dehydrogenation of low-carbon paraffin and be denoted as S.It examines
It comments condition with embodiment 1, the results are shown in Table 2.
[embodiment 20]
Weigh 8.43gSBA-15 and 1g Al2O3Carrier pours into 200mL deionized water stir 1 hour after, weigh 1.081g
Ammonium ceric nitrate and 0.212g zirconium nitrate are dissolved in respectively in 50mL deionized water, are then uniformly mixed the two, pour into aluminium oxide and
In the mixed liquor of water, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.Product aging 2 is small
When, filter cake is obtained with 2L water filtering and washing, it is small in 580 DEG C of Muffle kiln roastings 20 by filter cake after 90 DEG C are 16 hours dry
When to get Ce0.8Zr0.2O2-Al2O3- SBA-15 carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, stir
It is lower to be added in above-mentioned carrier, be uniformly mixed, 30 DEG C impregnate 12 hours, then 90 DEG C dry 16 hours up to catalyst precarsor,
It is denoted as I.The potassium nitrate of the chloroplatinic acid and 0.026g that weigh 0.159g is dissolved in 10mL water, is added with stirring in I, is uniformly mixed,
30 DEG C impregnate 12 hours, 90 DEG C drying 16 hours, 580 DEG C Muffle kiln roasting 20 hours i.e. obtain dehydrogenating low-carbon alkane be catalyzed
Agent is denoted as T.Examination condition the results are shown in Table 2 with embodiment 1.
[comparative example 1]
It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, be added with stirring in 9.76g alumina support, mix
Close uniformly, 30 DEG C impregnate 12 hours, then 90 DEG C dry 16 hours up to catalyst precarsor, be denoted as I.Weigh the chlorine of 0.159g
The potassium nitrate of platinic acid and 0.207g are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 30 DEG C impregnate 12 hours, and 90 DEG C dry
Dry 16 hours, catalyst for dehydrogenation of low-carbon paraffin was obtained within Muffle kiln roasting 20 hours at 580 DEG C, is denoted as U.Examination condition is the same as real
Example 1 is applied, the results are shown in Table 2.
[comparative example 2]
It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, be added with stirring in 9.84g alumina support, mix
Close uniformly, 30 DEG C impregnate 12 hours, then 90 DEG C dry 16 hours up to catalyst precarsor, be denoted as I.Weigh the chlorine of 0.159g
Platinic acid is dissolved in 10mL water, is added with stirring in I, be uniformly mixed, 30 DEG C impregnate 12 hours, 90 DEG C drying 16 hours, at 580 DEG C
It obtains catalyst for dehydrogenation of low-carbon paraffin within Muffle kiln roasting 20 hours, is denoted as V.Examination condition the results are shown in Table 2 with embodiment 1.
[comparative example 3]
Preparation and catalyst A form identical catalyst, and wherein complex carrier is prepared using infusion process.The preparation method comprises the following steps:
It weighs 1.081g ammonium ceric nitrate and 0.212g zirconium nitrate is dissolved in 10mL water, be added with stirring in the nano oxidized alumina supporter of 9.36g
30 DEG C impregnate 12 hours, 90 DEG C drying 16 hours, 580 DEG C Muffle kiln roasting 20 hours to get Ce0.8Zr0.2O2-Al2O3It carries
Body.It weighs 0.19g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, be added with stirring in the above-mentioned carrier of 10g, be uniformly mixed, 30
DEG C dipping 12 hours, then 90 DEG C dry 16 hours up to catalyst precarsor, be denoted as I.Weigh 0.159g chloroplatinic acid and
The potassium nitrate of 0.207g is dissolved in 10mL water, is added with stirring in I, is uniformly mixed, and 30 DEG C impregnate 12 hours, and 90 DEG C of dryings 16 are small
When, at 580 DEG C, i.e. obtaining catalyst for dehydrogenation of low-carbon paraffin is denoted as W within Muffle kiln roasting 20 hours.Examination condition with embodiment 1,
It the results are shown in Table 2.
Table 1
Table 2
[embodiment 21~29]
The catalyst that embodiment 1 is prepared is used for dehydrogenating low-carbon alkane, reaction raw materials are propane, and reaction raw materials are one
Propylene is obtained with catalyst haptoreaction under fixed condition；Reaction condition and evaluation result are shown in Table 3.
Table 3
[comparative example 4]
Catalyst regeneration stability contrast
It is de- that 0.5g catalyst A, 0.5g catalyst U, 0.5g catalyst V and 0.5g catalyst W progress iso-butane is weighed respectively
Hydrogen evaluation, the results are shown in Table 4 after reacting 1h.
Table 4
Claims (10)
1. one kind is used for catalyst for dehydrogenation of low-carbon paraffin, in terms of catalyst weight number, including following components:
A) 0.1~5 part of Pt or its oxide；
B) 0.1~5 part of alkali metal or its oxide；
C) 0.1~5 part of Sn or its oxide；
D) 0.1~10 part of Ce-M-O solid solution, M are Zr and Ti；
E) 80~99 parts of carrier Ss, S are selected from least one of aluminium oxide, silica or molecular sieve.
2. being used for catalyst for dehydrogenation of low-carbon paraffin according to claim 1, it is characterised in that with low-carbon alkanes catalyst weight
The number of number meter, Pt or its oxide is 0.1~2.5 part.
3. being used for catalyst for dehydrogenation of low-carbon paraffin according to claim 1, it is characterised in that with low-carbon alkanes catalyst weight
The number of number meter, alkali metal or its oxide is 0.5~2 part.
4. being used for catalyst for dehydrogenation of low-carbon paraffin according to claim 1, it is characterised in that with low-carbon alkanes catalyst weight
The number of number meter, Sn or its oxide is 0.1~2.5 part.
5. being used for catalyst for dehydrogenation of low-carbon paraffin according to claim 1, it is characterised in that Ce-M-O solid solution, with lower alkanes
Hydrocarbon catalyst parts by weight meter, number are 1~5.
6. according to claim 1 be used for catalyst for dehydrogenation of low-carbon paraffin, it is characterised in that with molar ratio computing Ce:M be (1~
99): 1.
7. being used for catalyst for dehydrogenation of low-carbon paraffin according to claim 1, it is characterised in that carrier S is γ-Al2O3、SiO2、
At least one of ZSM-5, SAPO-34, SBA-15 and MCM-41.
8. being used for catalyst for dehydrogenation of low-carbon paraffin according to claim 1, it is characterised in that with Pt in molar ratio computing catalyst:
Sn is (0.01~5): 1.
9. the preparation method of catalyst for dehydrogenation of low-carbon paraffin according to any one of claims 1 to 8, comprising the following steps:
A) after the carrier S of content needed for weighing is poured into suitable deionized water and stir 0.5~10 hour, required content is weighed
The soluble-salt of Ce and M is dissolved in respectively in suitable deionized water, is then uniformly mixed the two, pours into the mixing of carrier and water
In liquid, after continuing stirring 0.5~10 hour, it is slowly dropped into pH adjusting agent under continuous stirring until pH is 7~10；Product is old
Change, filter and wash, dry, roasting and obtain the complex carrier of Ce-M-O solid solution and S；
B) soluble-salt of the desired amount of Sn is dissolved in suitable hydrochloric acid solution, addition a step obtains compound under stiring
It in type carrier, is uniformly mixed, 10~80 DEG C impregnate 1~24 hour, dry, roast to obtain catalyst precarsor I；
C) soluble-salt of the desired amount of Pt and alkali metal are dissolved in suitable water, the catalyst of b step is added under stiring
Precursor I is uniformly mixed, and 10~80 DEG C impregnate 1~24 hour, is dried, is roasted to obtain catalyst for dehydrogenation of low-carbon paraffin.
10. any one of claim 1~8 catalyst is used for dehydrogenating low-carbon alkane, reaction raw materials are propane or iso-butane,
Reaction condition are as follows: low-carbon alkanes and hydrogen volume ratio are 10:1~1:1, and reaction temperature is 400 DEG C~600 DEG C, reaction pressure 0
~1MPa, alkane mass space velocity are 3.0~8.0h-1, reaction raw materials and the catalyst haptoreaction obtain propylene or isobutene.
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| CN109289847B (en) * | 2017-07-24 | 2020-06-09 | 中国石油化工股份有限公司 | Catalyst for catalyzing propane dehydrogenation reaction, preparation method thereof and method for preparing propylene by propane dehydrogenation |
| CN109289899B (en) * | 2017-07-24 | 2019-11-12 | 中国石油化工股份有限公司 | The method of composite material and preparation method and catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
| CN109289935B (en) * | 2017-07-24 | 2019-11-12 | 中国石油化工股份有限公司 | The method of complex mesoporous material and preparation method thereof and catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
| CN112547061A (en) * | 2019-09-25 | 2021-03-26 | 中国石油化工股份有限公司 | Catalyst for preparing propylene by propane dehydrogenation and preparation method thereof |
| CN113877577B (en) * | 2020-07-02 | 2024-01-30 | 中国石油化工股份有限公司 | Catalyst, preparation method thereof and method for improving alkane conversion rate |
| CN112206816B (en) * | 2020-10-13 | 2021-07-27 | 西南化工研究设计院有限公司 | Composite molecular sieve catalyst for preparing olefin by propane dehydrogenation and preparation method thereof |
| CN114425316B (en) * | 2020-10-15 | 2024-01-30 | 中国石油化工股份有限公司 | Carrier and preparation method thereof, alkane dehydrogenation catalyst and preparation method and application thereof |
| CN115232904B (en) * | 2021-04-23 | 2023-11-24 | 中国石油大学(北京) | Method for producing sponge iron |
| CN115487854B (en) * | 2021-06-18 | 2023-07-21 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst and preparation method and application thereof |
| CN115608405B (en) * | 2021-07-16 | 2024-02-20 | 中国石油化工股份有限公司 | Millimeter-sized spherical composite carrier, dehydrogenation catalyst, and preparation methods and applications thereof |
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